Hair care composition

ABSTRACT

Hair care compositions containing a synergistic mixture of three anti-free-radical agents selected from (a) ascorbic acid, its salts and esters; (b) tocopherol and its esters, such as tocopherol acetate; and (c) herbal extracts selected from  morus alba, origanum vulgare, panax ginseng, rosmarinus officinalis, camellia sinensis  and grape seed extract in a suitable diluent or carrier. Preferred synergistic mixtures are  Origanum vulgare , sodium ascorbyl phosphate and  morus alba. Origanum vulgare , sodium ascorbyl phosphate and  panax ginseng. Panax ginseng, morus alba  and  Origanum vulgare . Sodium ascorbyl phosphate,  morus alba  and  camellia sinensis . Sodium ascorbyl phosphate,  morus alba  and grape seed  Origanum vulgare, panax ginseng  and  rosmarinus officinalis.

This application is the U.S. national stage entry of InternationalApplication No. PCT/EP00/07196, filed Jul. 28, 2000, which claimspriority to British Application No. 9917729.7, filed Jul. 28, 1999, andincorporates these applications by reference in their entirety.

The present invention relates to hair care compositions havingprotecting and conditioning properties and to methods of using suchcompositions to treat hair.

The hair is exposed to a number of environmental challenges. Suchexposure can generate free-radicals, especially on exposure to sunlightand/or heat, and presence of high concentrations of free radicals isgenerally seen as undesirable in a toiletries composition to be used onthe hair. Free radicals, which are generated by factors such as UVradiation (present in sunlight), heat and/or by chemical reaction, areimplicated in the process of damage to hair, reduction in shine, poorfeel, and fading of hair colour.

There are a number of haircare compositions, commercially available,which seek to minimise the damage to the hair by the inclusion ofcertain agents. In particular materials such as vitamins and herbalextracts have widely been known to reduce the formation offree-radicals. However to achieve good efficiency high levels of thesematerials have to be used and this can result in dark aestheticallyunpleasing products that can stain the hair

The hair care compositions of the present invention have been shown toprotect the hair more effectively from free radicals and arecosmetically and aesthetically more suitable than known hair carecompositions. Therefore the hair care compositions of the presentinvention may be used to provide improved protection against damage tohair caused by exposure to factors such as sunlight, environmentaland/or atmospheric pollution, heat from styling the hair and/or chemicaltreatment of the hair (for example curling, perming, straightening,dyeing and/or bleaching). The hair care compositions of the presentinvention may comprise conventional hair care products and/or specifichair protection products which may be used for example as protectivepre-treatments prior to heat or chemical treatment of the hair.

The term “hair care composition” as used herein includes so-called “hotoil” treatments, shampoos, conditioners, hair dyes, mousses, foams,gels, creams, waxes, masks, muds, semi-solid structured styling pastes(also known as putties), styling sprays, lotions and rinses, allsuitable for use on the hair of animals, preferably on human hair, mostpreferably hair on the human head.

Therefore broadly according to the present invention there is provided ahair care composition containing a combination of anti-free-radicalingredients that when combined together give a synergistic improvementin activity allowing improved protection and condition to be providedfor the hair without the drawback of aesthetically unpleasant productappearance and the chance of hair staining.

The present invention provides hair care compositions containing asynergistic mixture of three anti free radical agents selected from (a)ascorbic acid, its salts and esters, particularly sodium ascorbylphosphate, magnesium ascorbyl phosphate and ascorbyl palmitate (b)tocopherol and its esters, such as tocopherol acetate and (c) herbalextracts, particularly morus alba, such as that available under thetrade name “Mulberry Concentrate” from Aston Chemicals; origanumvulgare, such as that available under the trade name “Pronalen OriganumHSC” from S Black Ltd; panax ginseng, such as that available under thetrade name “Ginseng 1.1 extract 4294” from S Black Ltd; rosmarinusofficinalis, such as that available under the trade name Herbal RosemaryWS from Chesham Chemicals or Pronelen Rosemary extract from S.BlackLtd]; camellia sinensis such as that available under the trade name“Herbal Extract Green Tea 75% Solids” from Nichimen Europe; and grapeseed extract such as that available under the trade name Grape SeedExtract WS from S.Black Ltd. In combination with a suitable diluent orcarrier. The agents used in the present invention are already known fortheir individual ability to quench free radicals and prevent oxidativedamage to the hair. However the present invention discloses that certaincombinations of these agents have an efficacy much greater thanexpected. This has been demonstrated experimentally.

The commercially available sources of the anti free-radical agents usedin the present invention consist of the anti free-radical agents butthese may also comprise diluents and/or carriers. Thus there may be someconfusion as to the actual level of agent within a commerciallyavailable product. Accordingly, the amounts of anti free-radical agentsused in the present invention are expressed as dry weights, asunderstood by a man skilled in the art.

The total amount of anti-free radical agents present in the compositionmay range from 0.003% to 10% by weight. Where the synergistic mixture ofanti free-radical agents is comprised solely of herbal extracts, then apreferred total amount of anti free-radical agents is 0.005% to 1%w/w,most preferably 0.01% to 0.6% by weight of the composition.

Preferably, the individual anti-free-radical agents that comprise thesynergistic mixtures may be present in an amount of from about 0.001% toabout 10% by weight, more preferably from about 0.003% to about 5% byweight, most preferably 0.004 to 0.2% by weight of the composition.

Particularly preferred synergistic combinations of anti free-radicalagents suitable for inclusion in a hair care composition are:

Origanum vulgare, sodium ascorbyl phosphate and morus alba.

Origanum vulgare, sodium ascorbyl phosphate and panax ginseng.

Panax ginseng, morus alba and origanum vulgare.

Sodium ascorbyl phosphate, morus alba and camellia sinensis.

Sodium ascorbyl phosphate, morus alba and grape seed.

Origanum vulgare, panax ginseng and rosmarinus officinalis.

A hair care composition containing a synergistic combination of antifree-radical agents has a multitude of advantages. Such antifree-radical agents are usually highly coloured. If they are usedindividually in amounts necessary to be totally effective, it, is likelythat the hair care composition would stain both skin and clothes andwould dye the hair. Further, even at lower levels the agents give thecomposition a cosmetically unacceptable appearance. Thus mostconventional hair compositions use less of an anti free-radical agentthan necessary to provide total protection. With the present inventionbecause of the increased efficacy of the synergistic mixture ofanti-free radical agents it is possible to include the anti free-radicalagents in sufficient amounts to provide an effective defence against theaction of free radicals. Thus use of the composition will give the usershair improved shine, feel, manageability, flexibility, colour and willhelp protect the hair from damage. All this is provided without theaforementioned disadvantages of staining, dyeing and unacceptablecosmetic appearance.

Alternatively, if the same level of protection as a conventionalformulation is required, then the increased efficacy of the synergisticmixture of anti free-radical agents means that the composition willrequire much lower quantities of the anti free-radical agents than aconventional formulation. Not only are any problems with highly colouredformulations reduced (staining, dyeing, cosmetic appearance), but thecost of the formulation is likely to be cheaper as well.

To further reduce the generation of free-radicals by the UV radiation insunlight, compositions of the present invention may further comprise anyacceptable sunscreening agent (that is an agent which acts to absorband/or reflect UV radiation present in sunlight) and which would beacceptable for use in a hair-care composition (for example suitable foruse on the human head). Such sunscreening agents may comprise inorganicsunscreens (for example zinc oxide and/or titanium dioxide preferably ofmicrofine (<100 nm) particle size) and/or organic sunscreens (forexample p-aminobenzoic acids, esters and derivatives, methoxycinnamateesters, benzophenones [such as benzophenone-4 {available commerciallyunder the trade name Uvinul MS40}]; dibenzoylmethanes and/or salicylateesters). The sunscreening agents may be present in an amount of fromabout 0.1% to about 10% by weight of the composition.

Further components may be added to the hair care composition as iswell-known to those skilled in the art.

For example, preservatives may be added to the composition such as2-bromo-2-nitropropane-1,3-diol (bronopol, which is availablecommercially under the trade name Myacide RTM), benzyl alcohol,diazolidinyl urea, imidazolidinyl urea, methyl paraben, phenoxy ethanol,propyl paraben, sodium methyl paraben and sodium propyl paraben,suitably in an amount of from about 0.01% to about 10% by weight of thecomposition.

Thickeners and viscosity modifying agents may be added to thecomposition, such as amine oxides, block polymers of ethylene oxide andpropylene oxide (for example, those available from BASF Wyandotte underthe trade name “Pluronic” RTM), ethoxylated fatty alcohols, cellulosicderivatives such as hydroxypropylmethyl cellulose, salt (NaCl), phthalicacid amide, polyvinyl alcohols and fatty alcohols, suitably in an amountof from about 0.5% to about 10% by weight of the composition.

Sequestering agents may be added to the composition, such asethylenediamine tetraacetic acid and salts thereof, suitably in anamount of from about 0.005% to about 0.5% by weight of the composition.

The composition may also include resins such as:octylacrylamide/acrylates/butylaminomethacrylate copolymer (availableunder the trade name Amphomer RTM); ethyl ester of polyvinylmethyl(hereinafter known as PVM)/methylacrylate (hereinafter known as MA)copolymer (available under the trade name Ultrahold 8A RTM); vinylacetate (hereinafter known as VA)/crotonates/vinyl neodecanate copolymer(available under the trade name Adhesive 28-2930 NAL);acrylates/acrylamide copolymer (available under the trade name GantrezES225 RTM); vinyl acetate/crotonic acid/vinyl propionate copolymer(available under the trade name Luviset CAP RTM); polyvinylpropionate(hereinafter known as PVP)/VA/vinylpropionate copolymer (available underthe trade name Laviskol VAP RTM); octylacrylamide/acrylate copolymer(available under the trade names Versatyl 90 RTM or Lovocryl 47 RTM);vinyl caprolactam/PVP/dimethylaminoethyl methacrylate copolymer(available under the trade name (H₂O LD EP-1); PVM/MA copolymer(available under the trade name Gantrez RTM); and vinyl acetate/butylmaleate/isobomyl acrylate copolymer (available under the trade nameAdvantage CP RTM), These resins may be present suitably in an amount offrom about 0.1% to about 10% by weight of the composition.

The composition, may also include slip aids such as phenyl trimethicone,suitably in an amount of from about 0.1% to about 10% by weight of thecomposition.

The composition may also include vitamins such as biotin, suitably in anamount of from about 0.01% to about 1.0% by weight of the composition.

The composition may also include waxes such as cocoa butter suitably inan amount of from about 1% to about 99% by weight of the composition.

The composition may also include gelling agents such as PVM, MA, or adecadiene crosspolymer (available under the trade name Stabilez 06),suitably in an amount of from about 0.1% to about 2% by weight of thecomposition.

The composition may also comprise suitable, cosmetically acceptablediluents, carriers and/or propellants such as dimethyl ether.

The composition may also include pearlising agents such as stearicmonoethanolamide, suitably in an amount of from about 0.01% to about 10%by weight of the composition.

Perfumes may be added suitably in an amount of from about 0.01% to about2% by weight of the composition, as may water soluble dyes such astartrazine, suitably in an amount of from about a trace amount (such as1×10⁻⁵%) to about 0.1% by weight of the composition.

The composition may also include pH adjusting agents such as sodiumhydroxide, aminomethyl propanol, triethanolamine, suitably in an amountof from about 0.01% to about 10% by weight of the composition.

The composition may be buffered by means well known in the art, forexample by use of buffer systems comprising succinic acid, citric acid,lactic acid, and acceptable slits thereof, phosphoric acid, mono- ordisodium phosphate and sodium carbonate. Suitably, the composition mayhave a pH between about 3 and about 10, preferably between about 4 andabout 8.

The composition may also include an antidandruff agent such as salicylicacid or zinc pyrithione or octopyrox suitably in an amount of from about0.1% to about 5% by weight of the composition.

Surfactants may be included, such as cosmetically acceptable salts ofalkyl ether sulphates, alkyl and alkylamidoalkyl betaines, ethoxylatedalcohols, polyethyleneglycol carboxylates, acceptable salts of alkylsulphates (such as ammonium lauryl sulphate), acceptable salts of alkylether sulphates (such as ammonium laureth sulphate or sodium laurethsulphate), sulphosuccinates (such as disodium laureth sulphosuccinate),amphoacetates and amphodiacetates (such as disodium cocoamphodiacetate),alkylpolyglucosides and alcohol sulphonates.

In accordance with a further aspect of the present invention there isprovided a method of treating hair (for example washing, conditioningand/or styling hair) by application to the hair of a composition asdescribed herein.

The invention will be illustrated with reference to the non-limitingtests and formulation examples described hereinafter:

EXAMPLE 1 Hair Conditioner

Ingredients % W/W Aqua to 100 Cetyl alcohol 3 Cetrimonium chloride 0.759Hydroxyethylcellulose 0.6 Propylene glycol 0.493 Panthenol 0.375 Parfum0.3 Benzophenone-4 0.2 Sodium chloride 0.15 Wheat amino acids 0.14Amodimethicone 0.105 Alcohol denat. 0.095 Dimethicone propyl PG-betaine0.09 Citric acid 0.026 Tetrasodium EDTA 0.02 Trideceth-10 0.0045Origanum vulgare 0.009 Panax ginseng 0.006 Morus alba 0.0046

The EDTA and hydroxyethylcellulose were added to the water and mixedusing a homogeniser to hydrate the polymer. Citric acid, benzophenoneand cetrimonium chloride were added. This was then heated to 70° C.

Cetyl alcohol was heated to 70° C. in a separate vessel and was thenadded to the aqeuous mixture using a homogeniser. The mixture was thencooled to below 40° C. using a propeller stirrer. The remainingmaterials including the antioxidant complex were then added and theproduct was made to weight with purified water.

EXAMPLE 2 Intensive Conditioner

Ingredients % W/W Aqua to 100 Cetearyl alcohol 4.6 Arachidyl propionate2 Dimethicone 2 Panthenol 1.5 Stearamidopropyl dimethylamine 1.5Hydroxyethylcellulose 0.75 Amodimethicone 0.7 Citric acid 0.503Cetrimonium chloride 0.435 PEG-20 stearate 0.4 Parfum 0.3 Propyleneglycol 0.29 Benzophenone-4 0.2 Sodium chloride 0.15 Wheat amino acids0.14 Polyquaternium-39 0.1 Alcohol denat. 0.095 Trideceth-10 0.03 BHT0.025 Isopropyl alcohol 0.02 Tetrasodium EDTA 0.02 Origanum vulgare0.009 Panax ginseng 0.006 Morus alba 0.0046

The EDTA and hydroxyethylcellulose were added to the water and mixedusing a homogeniser to hydrate the polymer. The citric acid andcetrimonium chloride were added and mixed using a propeller stirrer. Themixture was then heated to 70° C. In a separate vessel, the waxes,dimethicone and BHT were mixed and heated to 70° C. until melted anduniform. This mixture was then was added to the aqueous mixture and thiswas mixed until uniform. The resulting mixture was then cooled to below40° C. with stirring and the remaining materials including theantioxidant complex were then added and the product was made to weightusing purified water.

EXAMPLE 3 Leave in Conditioner

Ingredients % W/W Aqua to 100 PEG-40 hydrogenated castor oil 2Dipropylene glycol 1 Phenoxyethanol 0.85 Parfum 0.4 Panthenol 0.375Propylene glycol 0.29 Methylparaben 0.2 Benzophenone-4 0.2 Alcoholdenat. 0.095 Polyquaternium-10 0.091 Sodium chloride 0.3 Wheat aminoacids 0.028 Sodium hydroxide 0.026 Origanum vulgare 0.009 Panax ginseng0.006 Morus alba 0.0046

The polyquaternium-10 was added to the water and hydrated using apropeller stirrer. The methylparaben was pre-dispersed in thedipropylene glycol, gently heated to melt and then added to the hydratedpolyquaternium-10 mixture. The remaining materials including theantioxidant complex were then added and the product was mixed and madeto weight with purified water.

EXAMPLE 4 Gentle Shampoo

Ingredients % W/W Aqua to 100 Sodium laureth sulfate 8.25 Cocamidopropylbetaine 2.8 Sodium chloride 1.794 Cocamide DEA 1.63 PEG-6 cocamide 1Parfum 0.5 Panthenol 0.375 Propylene glycol 0.29 Benzophenone-4 0.2Glycerin 0.2 Phenoxyethanol 0.162 Wheat amino acids 0.14 Alcohol denat.0.095 Citric acid 0.05 Methyldibromo glutaronitrile 0.04 TetrasodiumEDTA 0.02 Origanum vulgare 0.009 Panax ginseng 0.006 Morus alba 0.0046

EDTA, sodium chloride, citric acid and benzophenone-4 were added to thewater. This was followed by the addition of sodium laureth sulfate,methyldibromo glutaronitrile, wheat amino acids and the antioxidantcomplex. PEG-6 cocamide and cocamide DEA were heated gently untilliquified. The parfum was added and mixed. This was then added to theabove mixture. The cocamidopropyl betaine and remaining materials werethen added and mixed. The product was made to weight using purifiedwater.

EXAMPLE 5 Anti-Dandruff Shampoo

Ingredients % W/W Aqua to 100 Sodium laureth sulfate 5.9 Disodiumlaureth sulfosuccinate 4 Laureth-3 3 Cocamidopropyl betaine 2.45 Sodiumchloride 1.926 Dipropylene glycol 1 Parfum 0.5 Piroctone olamine 0.5Panthenol 0.375 Propylene glycol 0.29 Disodium phosphate 0.25Benzophenone-4 0.2 Wheat amino acids 0.14 Alcohol denat. 0.095 Citricacid 0.063 Tetrasodium EDTA 0.02 Preservative 0.2 Origanum vulgare 0.009Panax ginseng 0.006 Morus alba 0.0046

EDTA, citric acid and benzophenone-4 were mixed into the water. Sodiumlaureth sulfate, disodium laureth sulfosuccinate, dipropylene glycol,disodium phosphate, wheat amino acids and the antioxidant complex wereadded and the product was stirred until uniform. The piroctone olaminewas dispersed in the parfum and added to the laureth-3. This mixture wasadded to the bulk and stirred. The remaining materials were then addedand the product was made to weight with purified water.

EXAMPLE 6 Anti-Chlorine Shampoo

Ingredients % W/W Aqua to 100 Sodium laureth sulfate 7.6 Cocamidopropylbetaine 2.8 Sodium chloride 1.694 Laureth-3 1 Phenoxyethanol 0.852Parfum 0.5 Disodium phosphate 0.4 Panthenol 0.375 Propylene glycol 0.29Methylparaben 0.2 Benzophenone-4 0.2 Wheat amino acids 0.14Propylparaben 0.1 Sodium thiosulfate 0.1 Alcohol denat. 0.095 Sodiumhydroxide 0.06 Sodium phosphate 0.06 Tetrasodium EDTA 0.02 Origanumvulgare 0.009 Panax ginseng 0.006 Morus alba 0.0046

Benzophenone, sodium chloride, sodium phosphate, disodium phosphate andEDTA were added to the water and mixed. Sodium laureth sulfate,phenoxyethanol, panthenol, wheat amino acids and the antioxidant complexwere then added and stirred. The preservatives were pre-mixed in thelaureth-3 and heated slightly to melt the powders. This was added to theproduct. The remaining materials were added and the product was made toweight using purified water.

EXAMPLE 7 Hair Gel

Ingredients % W/W Aqua to 100 Cyclomethicone 6.6 Dimethiconol 0.9Phenoxyethanol 0.8 Propylene glycol 0.79 Panthenol 0.75 Carbomer 0.7Aminomethyl propanol 0.4 Benzophenone-4 0.2 Parfum 0.2 Alcohol denat.0.095 Tetrasodium EDTA 0.05 Sodium chloride 0.03 Wheat amino acids 0.028Origanum vulgare 0.009 Panax ginseng 0.006 Morus alba 0.0046

EDTA and benzophenone-4 were added to the water using an homogeniser.The carbomer was added and hydrated with continued homogenising. Thephenoxyethanol, cyclomethicone, dimethiconol, propylene glycol andpanthenol were then added and mixed until homogenous. The remainingmaterials including the antioxidant complex were added and the bulk washomogenised until uniform and the product was made to weight usingpurified water.

EXAMPLE 8 Semi-solid Structured Styling Paste for Hair

This type of product is also known as a hair putty

Ingredients % W/W Aqua to 100 Cetearyl alcohol 10.9 Lanolin 7 PVP 6Paraffin 6 PVP/VA copolymer 5.7 Carnauba 3 Petrolatum 2Polyquaternium-11 2 PEG-20 stearate 1.9 Paraffinum liquidum 1 Propyleneglycol 0.8 Phenoxyethanol 0.6 Dimethicone 0.5 Panthenol 0.375Cetrimonium chloride 0.35 Dimethicone propyl PG-betaine 0.225Benzophenone-4 0.2 Methylparaben 0.12 Alcohol denat. 0.095 Origanumvulgare 0.009 Panax ginseng 0.006 Morus alba 0.0046

The PVP/VA copolymer, PVP and benzophenone-4 were added to the water andstirred until homogenous. This was then heated to 70° C. In a separatevessel, the waxes were mixed and heated to 70° C. until all materialshad melted. The hot waxes were then added to the aqueous mixture andmixed using a propeller stirrer until homogenous. The mixture was thencooled to below 60° C. and the remaining materials, including theantioxidant complex were then added and the product was stirred untiluniform. The product was made to weight using purified water.

EXAMPLE 9 Moisturising Conditioner

Ingredients % W/W Aqua to 100 Cetyl alcohol 4 Dimethicone 2Hydroxyethylcellulose 0.8 Cetrimonium chloride 0.765 Panthenol 0.75Propylene glycol 0.64 Parfum 0.3 Benzophenone-4 0.2 Amodimethicone 0.175Dimethicone propyl PG-betaine 0.15 Sodium chloride 0.15 Wheat aminoacids 0.14 Alcohol denat. 0.095 Citric acid 0.026 Tetrasodium EDTA 0.02Trideceth-10 0.009 Origanum vulgare 0.009 Panax ginseng 0.006 Morus alba0.0046

EDTA and hydroxyethylcellulose were added to the water usinghomogenising to hydrate the polymer. The benzophenone-4 and Laureth-3were then added and the bulk was heated to 70° C. In a separate vessel,the cetyl alcohol was heated to 70° C. until melted and was then addedto the bulk and mixed with a homogeniser until uniform. The product wascooled and the remaining materials, including the antioxidant complexwere then added and mixed. The product was made to weight using purifiedwater.

EXAMPLE 10 Spray Gel

Ingredients % W/W Phase 1 Aqua to 100 PVP/VA copolymer 4.9 Isopropylalcohol 2.5 Propylene glycol 2.29 Glycerin 2 Panthenol 0.375Benzophenone-4 0.2 Sodium chloride 0.03 Wheat amino acids 0.028 Origanumvulgare 0.009 Panax ginseng 0.006 Morus alba 0.0046 Phase 2 PEG-40hydrogenated castor oil 1 Parfum 0.3 Phase 3 Alcohol denat. 45Dimethicone copolyol 1

The materials in phase 1 were mixed until uniform using a propellerstirrer. The materials in phase 2 were pre-mixed and added to phase 1.The materials in phase 3 were mixed and added to the bulk. The productwas made to weight using purified water.

EXAMPLE 11 Dry Scalp Shampoo

Ingredients % W/W Aqua to 100 Sodium laureth sulfate 7 Sodium chloride2.23 Cocamidopropyl betaine 1.96 Laureth-3 1 Panthenol 0.375 Propyleneglycol 0.29 Piroctone olamine 0.25 Benzophenone-4 0.2 Phenoxyethanol0.162 Wheat amino acids 0.14 Polyquaternium-39 0.1 Alcohol denat. 0.095Citric acid 0.06 Methyldibromo glutaronitrile 0.04 Tetrasodium EDTA 0.02Origanum vulgare 0.009 Panax ginseng 0.006 Morus alba 0.0046

EDTA, citric acid, benzophenone-4 and sodium chloride were added andmixed using a propeller stirrer until all materials were dissolved anduniform. The sodium laureth sulfate and piroctone olamine were thenadded and stirred until homogenous. The remaining materials, includingthe antioxidant complex were then added and the product was stirreduntil uniform and homogenous. The product was made to weight withpurified water.

EXAMPLE 12 Deep Cleaning Shampoo

Ingredients % W/W Aqua to 100 Sodium laureth sulfate 14.13 Sodiumchloride 2.72 Cocamidopropyl betaine 1.4 PEG-6 cocamide 1 Parfum 0.5Panthenol 0.375 Propylene glycol 0.29 Benzophenone-4 0.2 Phenoxyethanol0.162 Wheat amino acids 0.14 Alcohol denat. 0.095 Methyldibromoglutaronitrile 0.04 Citric acid 0.02 Tetrasodium EDTA 0.02 Origanumvulgare 0.009 Panax ginseng 0.006 Morus alba 0.0046

Citric acid, EDTA and sodium chloride were added to the water anddissolved. The benzophenone-4, sodium laureth sulfate, cocamidopropylbetaine, panthenol, methydibromo glutaronitrile, wheat amino acids andthe antoxidant complex were then added and mixed until the product wasuniform, using a propeller stirrer. The parfum was pre-dispersed in thePEG-6 cocamide and then added to the bulk. The product was made toweight using purified water.

EXAMPLE 13 Moisturising Shampoo

Ingredients % W/W Aqua to 100 Sodium laureth sulfate 8.24 Cocamidopropylbetaine 2.8 Cocamide DEA 1.63 Panthenol 1.5 Sodium chloride 1.5Laureth-3 1.194 Parfum 0.5 Propylene glycol 0.5 Polyquaternium-10 0.273Glycerin 0.2 Wheat amino acids 0.14 Alcohol denat. 0.095 Dimethiconepropyl PG-betaine 0.09 Citric acid 0.04 Tetrasodium EDTA 0.02 Origanumvulgare 0.009 Panax ginseng 0.006 Morus alba 0.0046

EDTA and polyquaternium-10 were added to the water and the polymer washydrated using an homogeniser. The citric acid, sodium chloride andbenzophenone-4 were added and stirred until uniform. The remainingmaterials, including the antioxidant complex were added individually andthe product was mixed using a propeller stirrer until homogenous. Theproduct was made to weight using purified water.

EXAMPLE 14 Extra Hold Hair Gel

Ingredients % W/W Aqua to 100 PVP/VA copolymer 1.9 Propylene glycol 1.29Carbomer 1 PEG-40 hydrogenated castor oil 1 Panthenol 0.375 Sodiumhydroxide 0.26 Parfum 0.2 Phenoxyethanol 0.16 Tetrasodium EDTA 0.15 Mica0.113 Cystine hydroxypropyl polysiloxane 0.1 Alcohol denat. 0.095Methyldibromo glutaronitrile 0.04 Sodium chloride 0.03 Wheat amino acids0.028 Benzophenone-2 0.025 Origanum vulgare 0.009 Panax ginseng 0.006Morus alba 0.0046 Method

EDTA, methyldibromo glutaronitrile, PVP/VA copolymer and carbomer wereadded to the water and mixed using a homogeniser to ensure that thepolymers were hydrated. With continued homogenising, the cystinehydroxypropyl polysiloxane was added and mixed into the product. Theremaining materials, including the antoxidant complex were addedindividually and mixed using a propeller strirrer until the product washomogenous.

EXAMPLE 15 Gentle Shampoo

Ingredients % W/W Aqua to 100 Sodium laureth sulfate 8.25 Cocamidopropylbetaine 2.8 Sodium chloride 1.794 Cocamide DEA 1.63 PEG-6 cocamide 1Parfum 0.5 Panthenol 0.375 Propylene glycol 0.29 Benzophenone-4 0.2Glycerin 0.2 Phenoxyethanol 0.162 Wheat amino acids 0.14 Alcohol denat.0.095 Citric acid 0.05 Methyldibromo glutaronitrile 0.04 TetrasodiumEDTA 0.02 Origanum vulgare 0.2 Panax ginseng 0.2 Morus alba 0.2

EDTA, sodium chloride, citric acid and benzophenone-4 were added to thewater. This was followed by the addition of sodium laureth sulfate,methyldibromo glutaronitrile, wheat amino acids and the antioxidantcomplex. PEG-6 cocamide and cocamide DEA were heated gently untilliquified. The parfum was added and mixed. This was then added to theabove mixture. The cocamidopropyl betaine and remaining materials werethen added and mixed. The product was made to weight using purifiedwater.

EXAMPLE 16 Gentle Shampoo

Ingredients % W/W Aqua to 100 Sodium laureth sulfate 8.25 Cocamidopropylbetaine 2.8 Sodium chloride 1.794 Cocamide DEA 1.63 PEG-6 cocamide 1Parfum 0.5 Panthenol 0.375 Propylene glycol 0.29 Benzophenone-4 0.2Glycerin 0.2 Phenoxyethanol 0.162 Wheat amino acids 0.14 Alcohol denat.0.095 Citric acid 0.05 Methyldibromo glutaronitrile 0.04 TetrasodiumEDTA 0.02 Origanum vulgare 0.2 Panax ginseng 0.2 Rosmarinus officinalis0.2

EDTA, sodium chloride, citric acid and benzophenone-4 were added to thewater. This was followed by the addition of sodium laureth sulfate,methyldibromo glutaronitrile, wheat amino acids and the antioxidantcomplex. PEG-6 cocamide and cocamide DEA were heated gently untilliquified. The parfum was added and mixed. This was then added to theabove mixture. The cocamidopropyl betaine and remaining materials werethen added and mixed. The product was made to weight using purifiedwater.

A number of trials were conducted to demonstrate the efficacy of thesynergistic combinations of anti-free radical agents.

In Vitro Tests

Linoleic acid (model skin and hair lipid) was incubated in the presenceof various antioxidants and antoxidant combinations and was exposed tobroad spectrum UVA/B to induce oxidation of the lipid. Followingextraction of the lipid into methanol, the amount of lipidhydroperoxides (free radical generated damage) formed were measured witha specific colorimetric biochemical test. The degree of inhibitionafforded by the antioxidants was thus measured and compared toirradiated vehicle controls.

The percentage inhibition of free radical mediated lipid peroxidationwhen compared to the vehicle alone are given below.

Antioxidants % inhibition Morus alba (ma) 0 Origanum vulgare (ov) 49Panax ginseng (pg) 5.7 Sodium ascorbyl phosphate (nap) 21 Grape seed(gs) 0 Camellia sinensis (cc) 19 Observed effect of nap/pg/ov 100Predicted effect of nap/pg/ov 75.7 Observed effect of nap/ma/ov 100Predicted effect of nap/ma/ov 70 Observed effect of nap/ma/cc 100Predicted effect of nap/ma/cc 40 Observed effect of nap/ma/gs 81Predicted effect of nap/ma/gs 21

Thus it can be seen that the observed inhibiting effect of using theabove combinations of antioxidants is greater than that which would beexpected from the sum of the contributions of the individual thusdemonstrating a synergistic effect.

In a second series of experiments using antoxidants collected in a laterseason gave the following results.

Antioxidant % inhibition morus alba (ma) 37 origanum vulgare (ov) 29rosmarinus officinalis (ro) 15 panax ginseng (pg) 10 Observed effect ofro/pg/ov 88 Predicted effect of ro/pg/ov 54 Observed effect of pg/ma/ov93 Predicted effect of pg/ma/ov 76

Thus it can be seen that the observed inhibiting effect of using theabove combinations of antioxidants is greater than that which would beexpected from the sum of the contributions of the individual thusdemonstrating a synergistic effect.

In Vivo Tests

Swatches of hair were bed at each end and then cut into two pieces. Oneof these pieces was used as a test and the other was used as a control.Each piece was washed with either the shampoo under test or a controlcontaining no anti-free-radical agents for one minute and then rinsed intepid water for 30 seconds. The swatches were then fixed on a plate andirradiated with broad spectrum UVA/B light for 8 hours in the HeredusSuntest plus to induce oxidation of the lipid. Samples of each swatch(0.12 g) were weighed out and placed in an epindorph tube. A 2:1 mixtureof chloroform and methanol (1 m) was added. The tubes were placed in acentrifuge tube, placed on a tumbula mixer and mixed for 2 hours in arefrigerator. The hair was removed and the solvent removed undernitrogen. The lipids were resolubilised by adding methanol (50 μl) andvortexing for 15 seconds. Aliquots (7.5 μl) were plated out intriplicate and assayed for the level of oxidised lipid using acommercially available specific colourimetric biochemical test (K-AssayLPO kit). Each test was repeated with 5 separate hair swatches and themean result for each of the 3 determinations for all five swatchesenabled the amount of oxidised lipid to be measured.

The composition of Example 1 containing morus alba (0.2%), origanumvulgare (0.2%) and panax ginseng (0.2%) showed an amount of oxidisedlipid of 113 nmol/ml compared to 181 nmol/ml for the control. Thereduction in the amount of oxidised lipid is therefore around 38%.

The composition of Example 8 containing morus alba (0.2%), origanumvulgare (0.2%) and panax ginseng (0.2%) showed an amount of oxidisedlipid of 372 nmol/ml compared to 553 nmol/ml for the control. Thereduction in the amount of oxidised lipid is therefore around 33%.

The composition of Example 15 containing morus alba (0.2%), origanumvulgare (0.2%) and panax ginseng (0.2%) showed an amount of oxidisedlipid of 482 nmol/ml compared to 731 nmol/ml for the control. Thereduction in the amount of oxidised lipid was around 34%.

The composition of Example 16 containing rosmarinus officinalis (0.2%),origanum vulgare (0.2%) and panax ginseng (0.2%) showed an amount ofoxidised lipid of 601 nmol/ml compared to 694 nmol/ml for the control.The reduction in the amount of oxidised lipid was around 13%.

Sensory Analysis

Swatches of hair treated with either base formulation or formulationscontaining antioxidants were assessed by an expert panel for factorssuch as shine. softness, static, ease of combing, gloss and overallfeel. Statistical analysis was used to determine whether antioxidantswere able to protect and enhance these properties.

The results showed an improvement in shine and feel.

1. Hair care composition comprising a synergistic mixture of threeanti-free-radical agents selected from the group consisting of (a)sodium ascorbyl phosphate or magnesium ascorbyl phosphate (b) morusalba; (c) origanum vulgare; (d) panax ginseng; (e) rosmarinusofficinalis; (f) camellia sinenis; and (g) grape seed extract; in asuitable diluent or carrier.
 2. The hair care composition of claim 1,wherein (A) is sodium ascorbyl phosphate.
 3. The hair care compositionof claim 1, wherein the total amount of anti-free radical agents presentranges from about 0.003 to about 10% by weight.
 4. The hair compositionof claim 1, wherein the total amount of anti-free-radical agents presentranges from 0.005 to about 1% by weight.
 5. The hair care composition ofclaim 1, wherein the total amount of anti-free-radical agents presentranges from about 0.01 to about 0.6% by weight.
 6. The hair carecomposition of claim 1 where the synergistic combination of anti-freeradical agents is one combination selected from the group consisting of:Origanum vulgare, sodium ascorbyl phosphate and morus alba; Origanumvulgare, sodium ascorbyl phosphate and panax ginseng; Panax ginseng,morus alba and origanum vulgare; Sodium ascorbyl phosphate, morus albaand grape seed; and Origanum vulgare, panax ginseng and rosmarinusofficinalis.
 7. A method of treating hair comprising applying to saidhair the hair care composition of claim
 1. 8. The composition of claim1, wherein the total amount of anti-free-radical agents present in saidcomposition is below the level that causes staining of skin or clothesor dyeing of hair.
 9. The composition of claim 1, wherein saidcomposition further comprises at least one sunscreen agent.
 10. Thecomposition of claim 1, wherein said composition further comprises atleast one pH adjusting agent.
 11. The composition of claim 1, whereinsaid composition further comprises at least one buffer system.
 12. Thecomposition of claim 1, wherein said composition further comprises atleast one antidandruff agent.
 13. The composition of claim 1, whereinsaid composition comprises origanum vulgare, sodium ascorbyl phosphateand morus alba.
 14. The composition of claim 1, wherein said compositioncomprises origanum vulgare, sodium ascorbyl phosphate and panax ginseng.15. The composition of claim 1, wherein said composition comprises panaxginseng, morus alba and origanum vulgare.
 16. The composition of claim1, wherein said composition comprises sodium ascorbyl phosphate, morusalba and grape seed.
 17. The composition of claim 1, wherein saidcomposition comprises origanum vulgare, panax ginseng and rosmarinusofficinalis.